Polyazo dyestuffs



Patented Aug. 12, 1952 :1 Philinpe Grandjean, Basel, Switzerland, ass ignor to-Sandoz; A; G. Basel, Switzerland, a Swiss .No Drawing, Application August 14, 1951, Serial No'. 241,895. tln switzerland August 17, 1950 .1 They present invention" relatesd to 'po-lyazq yestuirs. l

The primary object oi the present invention is the embodiment of anew group of polyazo dyestu fis characterized by diazoti zability, good drawing capaoity onto cotton and regenerated cellulose, and the property of yielding dyeings in a variety of shades of good fastness properties and dischargeability. This object. is=';-rea1ized,

according to this invention, by the group of dyestuffs which correspond to the formula Y NH;

wherein n is one of the integers() and 1, of R1 and R2 stands for radicals of'the benzene and naphthalene series, one a stands for -'-'SO3 H, the other a and each of both band both 0 stand I for hydrogen and halogen atoms and lower alkyl-, lower alkoxy hydroxy-, COOH-'. and SOaI-I- groups, Z stands for NHCO-'- ,and ,v'-N=N,

Xstands vfor hydrogen; lower alkyl or lower alkoxy, and Y stands for hydrogem -halogen,

lower alkyl or lower alkoxy. f.

These new dyestuffs are obtained by the action or a reducing agent on a dyestufl of the formula (Formula 1) 6 Claims (Cl. 260167) wherein n, R1, R2, a, b, e, Z, X'and Y have the previously-indicated significan'ces, wherebyi the 'N02 group is convertedte NH2. I 1 'The starting dyestufiscorresponding to Formula 1 (supra) maybe preiiared for exampleas r nan-lamina we formula 5 wherein 11,31, Re; a, a; 1c and- 'z have' the :preeeamgly-reciteds'ignificances is diazotized, the ob- 0f the formula.

t'ained diazo compound couplediwith an amine 0" (f ds?) wherein Ac 'stands for an acyl group of the'alibh'atic -series,'= s'uch {for" example" as a "iormyl, "acetyLfoxalyl or urethane group, which is readily hydrolyzable in acid medium, and X'has'the'prev viously indicated' significance, then the thusproduced p-aminoaio"dyestufi-treated with phosgene, the Ac grouphydroly'z'ed in such'mannere. g. by the action of a dilute mineralacid-while warming mi1dly'that the urea 'group is not-attacked, and'then the resultant o-aminoazo dye- .lstufi condensed with a benzoio' 'acidhalidesof the iormula f (Formula 3) wnieinir -ilas prey usly -indicated slg- (p A t rngti e yggt jgmmg 'dyestufr may be fpre'paired by id azotizi g a flm i l jif' t mii 3 wherein 11., R1, R2, a, b, c and Z have the precedingly-recited significances, coupling the obtained diazo compound in acid medium with an amine of the formula Y NO; o 1 NH azo dyestufi with phosgene."

Suitable amines of the formula :jo'r ruse; according. tothe present invention in:

making the starting dyestuffs of the Formula 1 (supra), comprise .aminobenzeneemonosulfonic acids, aminobenzeneedisnlfonic acids, aminormethylbenzene' sulfonic :acids, aminoeethylbenzene sulfonic acids, amino-chlorobenzenensulionic acids, aminoebromobenzene sulionic acids, aminonaphthalene-monosulfonic acids, aminonaphthalene-disulfonic acids, aminobenzoylamino-hydroxy-sulfo-benzene carboxylic acids, aminoazobenzene-monosulfonic acids, aminoazobenzene-disulfonic acids, aminoazomethylbenzenemonosulfonic acids, aminoazomethylbenzene-dii iee es am n aeeemp umi ine coupling a diazotizediarninehenzenesulfonic :acid -;oraminonaphthalene sulfonic acid with an amine of the benzene or naphthalene series, such for example as aminobenzene, l-amino-S-methylbenzene, l-amino-B-ethylbenzene, l-amino-2,5- dimethylbenzene, 1-amino-2-methoxy-5-methy1- benzene, l-amino-2',5-dimethoxybenzene, l-amino-2,5-diethoxybenzene, l-aminonaphthalene, l ammonaphthalene-fi-sulfonic acid, l-aminonaphthalene-'7 -s ulfonic acid, etc.

. -Suitable amines of Formula}, {supra} ioruse f iii-preparin the swi e-d e tu s d n w method (a), supra,- cemprise 3-formy1-amino-l.- aminobenzene, 3-acetyl-amino-1-aminobenzene, 3-oxalyl-amino-1-aminobenzene, 3-formyl-am'1- no l -amino-fi methylbenzene, BeacetyI-aminQPlamino-firemethylbenzeneg, -3-oxalyl-amino-l-aminn fi-methylbenzene, -3-iormyl-amino-1-anuno- =6+methoxybenzene 3-acetylamino-i-amino6- -methoxybenzene, 3-oxalyl-amino-l-amino-6- "methoxybenzene; 3-formyl-amino-1-amino-6- ethylbenzene, 3-acetyl-amino-l-ainino -fi-ethylbenzene, 3-oxalyl-amino-1-amino-6-ethylbenzene, 3-formyl-amino-l-amino-6-ethoxybenzene, 3-acetyl-amino l -amino-d ethoxybenzene, etc,

-' Suit'able benzoic acid halides of Formula 3 (supra) for preparing the starting dyestuffs according to method ,(a), supra, comprise.3 nitrobenzoyl chloride, i nitrobenz'oyl chloride, nitro- 3-methylbenzoyl chloride:4-nitro-3-ethylbenzoy1 chloride, fi-nitro-eme'thoxybenzoyl chloride, 3- mtro-4-ethoxybenzoyl chloride, 4-nitro-3-chlorobenzoyl chloride, 4-nitro-3-bromobenzoyl chloride, the corresponding benzoyl bromides, etc.

Suitable amines of Formula 4 (supra) for preparin the starting dyestuffs according to meth- (Formula 4) wherein X and Y have theaiforeindicated signifi canoes, and treating the thuseprepared stantive dyestuffs of Formula 1 into dyestuffs which draw onto, cotton and regenerated cellulose and, diazotized on the fiber and for instance developed with Z-hydroxynaphthalene or a phenylmethylpyrazolone, yield yellow, orange, red,

I bordeaux-red and brown dyeings which are very fast to washing and to light and are of good dischargeability.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended. to be solely illustrative' and not at all limitativeo In these examples, the parts and percentagesare by weight,

and the temperatures are. expressed in degrees .eentigrade 5.0.4 partse! the sodium-saltof the dyestuff of theformula' is "1" 11102 QSIOZH J2 3 are dissolved 1500 parts of water at and an aqueous solution of 12.5 parts of sodium sulfide are added to the resultant solution, The mixture is'maintained at IO- for about 1 hour, and then the reduced dyestufi is salted out withsodium chloride, filtered off and washed. The dyestufi is a yellow powder, and dyes cotton and regenerated cellulose in yellow shades of ood dischargeability. The resultant dyeings, after diazotization on the fiber and development with phenylmethylpyrazolone,is of very good iastness to washing.v The dyestufl corresponds to "the formula n e'stufl's with similar properties are obtained fwhen, while otherwise proceeding as described in the preceding paragraph, use is made of starting dyestuffs wherein, on the one hand, the com- =ponent derived from 1-amino-2,4 '-dimethylben- 'zene' fi-sulfonic acid is replaced by ail-equivalent of a component derived from one of the following:

1-aminobenzene-2-sulfonic acid, or 1-aminobenzene-3-sulfonic acid, or l-aminobenzene-4-sulfonic acid, or 1-amino-2 methylbenzene-4-sulfonic acid, or 1-amino-2eethylbenzene-4-sulfonic acid, or 1-amino-2-ethylbenzene-5-su1fonic acid, or? 1-amino-2chl0r0benzene-4-su1f0nic acid, or; 1-amino-2 bromobenzene-i-sulfonic acid, or" 1-amino 2,4 dichlorobenzene-fi-sulfonic acid, 4'

while, on jthe other hand, the 4-nitrobenz'oyl moietvderived from the -nitrobenzoyl chloride is replaced by an equivalent of a' corresponding moiety derived from one of the following:

, 3-nitrobenzoyl chloride,;or

4-nitro-3-methylbenzoyl chloride, or

- 4'- nitro-3 e'thylbenzoyl chloride; or.

3-nitro-4-methoxybenzoyl chloride; or 3-nitro-4-ethoxybenzoyl chloride, or 4-nitro-3-chlorobenzoyl chloride, or 4-nitro' 3'-bromobenzoyl chloride, or A corresponding bromide.

The formula of a representative alternative dyestufi thus producible is, for instance:

CHa

Example 2 I b 69.0 parts of the sodium salt of the dyestun of the formula are dissolved in 2000' partsof water at and .then admixed with an aqueoussolution; of 18 parts of sodium tetrasulfide, The mixture is stirred for about 1 hour at 80, the reduced 'dyestuff salted out with sodium chloride, filterediofl' and dried. The new dyestufi thus obtained is a yellow powder, which corresponds to the formula coon Q G Q B0111 V 'g 5J2; {and {dyes cottonand reenerated' celluloseiriy'd- 'lowshades V of good discliairgeabilityg; After di "aaqtization' on jthe fib'er'; and development with f'phenyln ethylpytazolone, the resultant gdyeings are-characterized by very good fastnesf's'to washing. Bydevelopment-with "2-hydrokynaphthalene, orange coloreddyeings with the same properties are obtained. I

Dyestufis with similar properties are obtained when, while otherwise proceeding as described in the preceding paragraph, use is made of starting dyestuffs wherein, on the one hand, the moiety derived from 4-(4'-amino 3 chloro benzoylamino) 1 hydroxy 6-sulfo-benzene-2;carboxylic acid is replaced byan equivalent of the corresponding moiety derived from 4-(3'.-amin'obenzoylamino) 1-hydroxy-6-sulfobenzene-2-carboxylic acid or from fi-(e' amino-benzoyiamino) -1-hydroXy-4-sulfo-benzene-Z-carboxylic "acid, while, onthe other hand, the 4-nitrobenzoyl moiety derived from the 4-nitrobenzoy1 chloride is replaced by an equivalent of a corresponding moiety derived from one of the nitrobenzoyl halides enumerated in the second paragraph of Example 1. The formula of a representative alternative dyestuffthus producible is, for instance:

excess? not; f

are dissolved in 2000 parts of water at 70 and-- .Lthen; admixed with an aqueous solution-o1 12.5 gar-ts or sodiumsulfide,- -}1he mixture is stirred ior about hour at {IO-3?; and the produced re- ;duced: dyestufi then salted out with sodium chlosi s in ensive a i Th ew; dm n .thus obtained cor-responds; he formula and is a yellow powder which dyes cotton and regenerated cellulose in yellow shades of good dischargeability. After diazotization on the fiber and development with phenylmethylpyrazolone, the obtained 'dyeings possess very good washiastness properties,

(a).- The: moiety derived from: 2-aminonaphthalene,4,8-disulfonic acid is-replaced by an equivalent of the corresponding moiety. derived from 2-aminonaphthalene-6,8-disulfonic acid or from 2-aminonaphthalene-5,7-disulfonic acid or from- 2-am-inonaphthalene fi-sulfonic acid or from 2-aminonaphthalene-8-sulfonic acid;

(b) The moiety derived from 3-acylamino-1- aminobenzene is replaced by an equivalent of the corresponding moiety derived from a 3-acy1amino-l-amino-G-methylbenzene or from a 3- acylamino-l-amino-6-ethy1benzene; and

c) The 4-nitrobenzoyl moiety derived from the 4-nitrobenzoyl chloride is replaced by an equivalent of a corresponding moiety derived from one of the nitrobenzoy] halides enumerated in the second paragraph of Example 1. The formula of a representative alternative dyestui! thus producible is, for instance:

Examples!" 69.6 parts of asti matism salt-of the dyestuff of the formula;

SOaH

i i co o 2 are dissolved in 1500 parts of water at and then admixed with an aqueous solution of 11.5 parts of sodium disulfide. The mixture is stirred for about /2 hour; and the resultant reduced dyestuflsa'lted out with sodium chloride, filtered off and dried. The new dyestuff, obtained as a Dyestufis with similar pronerties are obtained, '3 dark-brown powder, corresponds to the formula,

. r ,r I v when, while otherwise proceeding as described ,anddves cotton and regenerated cellulose in in the foregoing paragraph, use is made of start- I 7 fastness to light. After diazotization on the fiber ing dyestufis wherein:

brownshades ofvery good dischargeability and and development with 2-hydroxynaph'thalene; the enumerated inthe second paragraphlof Example.

dyeings are characterized'by very good fastness 1. The formula of'a representative alternativetowashing. dyestuff thus'producibleis,-for'instance .t v:. a

. I O CH: OH; NH

HI J2 Dyestuifs with similar properties are obtained Example 5 when, while otherwise proceeding as describedinf' the foregoing paragraph, use is made of starting 7446 parts of the tetrasodium salt of the dyedyestufis wherein: stufi of the formula (a) The moiety derived from 4-amino-1,1-azoare disso1ved;in-"2000 parts of water at 70 and; zene-3,4"-disulfonic acid is replaced by an equivthen an aqueous solution of 12.5 parts of sodium alent of the corresponding moiety derived'from sulfide is added. The mixture is stirred for about 5 Famine-1,1-azobenzene-4-sulfonic acid or from 1 hour at 7075,"whereupon the resultant reduced 4"-amino 2,3 dimethy1-- L1 5 azo]oenzene' dyestufl is saltedout with sodium chloride, fil- 4"=-su lfonic acid or from the aminoazo compound tered off and dried. It corresponds to the formula from diazotized l-aminobenzenel-sulfonic acid The new d'yestuff is a brown pow r; it d Cotand 1-aminonaphthalene-G-sulfonic acid or 1- ton and regenerated cellulose in brown shadeslaminonaphthalene-T-sulfonic acid; of good "dischargeability. After diazotization (b) The moiety derived from 3-acylamino-lthe fiber-and development with 2-hydroxynaphaminobenzene is replaced by an equivalent of the thalene, the resultant-dyeings P ssess very good corresponding moiety derived from a 3-acyl- 7 fastness to washing, v amlno-l-amino-G-methylbenzene or from a 3.-

: Dyestuffs with similar properties are olo-taine'd acylamino-6-methoxybenzene; and when, while otherwise proceeding .as described in i (c) The 4-nitro-3-methylbenzoyl moiety is rethe foregoing paragraph, use is e g g placed by an equivalent ofaoorresponding moiety I ing dyestufis wherein: w derived from one of the nitrobenzoyl halides 7-5 (a) The moiety derived from 2-aininonaph-..E

access? 1.1 thElEIlfifiB-adififlifflflifi acid is replaced by an equivalent of the. corresponding moiety derived form 2-aminonaphthaleneeLB-disulionic 7 acid or from 2-aminonaphthalene-5,'Z-disulfonic acid;

(b) The 1-amino-3-methylbenzene component (first azo component) is replaced by an equivalent of l-amino-2-methylbenzene component or of 1- Example 6 80 parts of the "tetrasodium s'alt'of the dyestu'if of FF? rmula r are dissolved in 2500 parts of water at other which anzaqueous solution of 12.5 parts sodium sulfide is added, the mixture stirred for 1 hour at 70-75", and the formed reduced dyestuff thereupon salted out with sodium chloride, filtered 01? and dried. The product corresponds to the formula QCH:

OCH: NH

it v v.

The new dyestuif is a brown powder; it dyes cotton and regenerated cellulose in violet-brown shades. After diazotization on the fiber and development with 2-hydroxynaphthalene, the obtained dyeings are of very good fastness to wash- Dyestufis with similar properties are obtained when, while otherwise proceeding as described in the foregoing paragraph, use is made of starting dyestuffs wherein:

(a) The component derived from 2-aminonaphthalene-5,7-disulfonic acid is replaced by an equivalent of a corresponding component derived from 2-aminonaphthalene-4,8-disulfonic acid or from 2-aminonaphthalene-6,8-disulfonic acid;

,-(b) The lamina-2,5-.dimethoxybenzene component (first azo component) is replaced by an equivalent of l-amino-Z-diethbxybenzene coinponent or of fl-amino zmethoxybenzene compo- I nent or of l-amino-3emethoxybenzene;compo- I nent or of 1-amino-2-methoxy-5-methylbenzene component or of 1-amino-2-ethoxy-5-methylbenzene component;

(0) The 3-acylamino-1-amino 6 methylbenzene component (second azo component) is replaced by an equivalent of a 3-acylamino-1- aminobenzene component or of a. 3-acylamino-1- amino-G-methoxybenzene component; and

(d) The 3-nitrobenzoy1 moiety is replaced by an equivalent of a corresponding moiety derived from one of the nitrobenzoyl halides enumerated in the second paragraph of Example 1. The

accolade;

formula of. a representative alternative dyestufi thus. producible is, for instance: .7

r NH:

; ra-i i Example 7 68.8 parts of the tetrasodium salt of the dyestuff of the formula.

(ROE:

H913 O CH:

(l)CHs ton and regeneratedcellulose in orange shades of good discharge'ability. Afte'f"diazotization on the fiber and development with 2-hydroxynaphthaleiie, the obtained dyeings are of very good wash fastnes.

when, while otherwise proceeding as described in the foregoing paragraph, use is made of starting dyestuffs wherein:

(a) The component derived from 2-aminonaphthalene-6,8-disulfonic acid is replaced by an equivalent of a corresponding; component derived from 2-aminonaphthalenel,8-msulfonic acid or from 2-aminonaphthalene-5,7edisulfonic acid;

(b) The 3 acylamino 1 amino 6 methoxybenzene component is replaced by an equivalent of a 3-acylamino-1-amino-6-ethoxybenzene component; and

(c) The 3, nitro- 4 methoiiybenzoyl moiety is replaced by an equivalent of a corresponding moiety derived from one of the nitrobenzoyl halides enumerated in the second paragraph of Example 1. .The formula of a representative alternative dyestuif thus, producible is, for instance:

F" NH Example 8 in 20.00 parts of water.

salt added and then allowed to cool to about The dyed material is well rinsed with water and then treated for hour in a cold bath with 2 parts of sodium nitrite and 5 parts of hydrochloric acid (30%) After rinsing with cold water, the material is entered into a cold development bath which contains 1 part of 1-phenyl-3-methyl-5-pyrazolone and 0.5 part of calcined sodium carbonate. The material is treated in this bath for hour and then thoroughly rinsed.

The thus-obtained yellow dyeing is of very goodffastness to washing and to light and of excellent dischargeability.

Having thus disclosed the invention what is claimed is:

1. A polyazo dyestufi which corresponds to the formula LLL r .17. I 3 :wherein n is one of the integers 0 and 1; each of R1 Dyestuffs withsimilar properties are obtained and R2 stands for a member selected from the group consisting of radicals of the benzene and naphthalene series, one a stands for -SO3H, the

other a and each-of both I) and both 0 stand for members selected from the group consisting of hydrogen and halogen atoms and lower alkyl-,

lower a1koxy-, hydroxy-, COOI-I- and SOsH- groups, Z stands .for a member selected from the group consisting of -+NHCO- and N=N--, X

stands for a member selected from the group consisting of hydrogen, lower alkyl and lower alkoxy, and Y stands for a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy.

The dyebath .is slowly; heated to boiling, 20 parts of calcined-Glaubers 

5. THE POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA: 